Elucidating Nonlinear Stress Relaxation in Transient Networks through Two-Dimensional Rheo-Optics

This study aims to elucidate the origin of nonlinear stress relaxation behaviors in transient networks using a systematically controlled model system consisting of the tetra-armed polyethylene glycols (Tetra-PEG slime) in conjunction with two-dimensional rheo-optics observations. Transient networks, characterized by their temporary cross-links, are extensively utilized in self-healing and robust materials. However, the molecular mechanisms governing their viscoelastic responses to large deformations have remained elusive. This is primarily due to the heterogeneous structures inherent in conventional transient networks and a scarcity of detailed experimental evaluations. By employing Tetra-PEG slime, which is distinguished by its regular structure with uniform strand lengths and functionalities, and the polarization imaging method, we overcome these obstacles. Our results reveal that the damping phenomena observed under large step strains arise from spatially heterogeneous relaxation, predominantly driven by network strand pullout. These insights lay a solid foundation for understanding the intricate rheological properties of transient networks.